Bituminous emulsions



Patented May 30, 195 9 EJNH'EQ STATES mm orrics BITUMINOUS EMULSIONS ration of Delaware No Drawing. Application July 31, 1946, Serial No. 687,531

10 Claims.

This invention relates to quick-breaking bituminous emulsions; more particularly, to quickbreaking asphalt emulsions.

Quick-breaking bituminous emulsions, as the term is used in the art and herein, are oil-in-water type emulsions of asphalt (residue from distillation of petroleum, and natural asphalt), coal tar, coal tar pitch and other liquid of heatliquefiable carbonaceous materials, which undergo rapid breakdown on contact with aggregates (rock, sand, gravel, soil, etc).

More narrowly defined, they are oil-in-water type emulsions of bituminous materials having high enough residue (55 to 70%) to be useful as road binders and the like, and undergoing not less than 60% breakdown on admixture with 35 mls. of 0.02 N calcium chloride in accordance with the procedure of A. S. T. M. D244-42 Demulsibility Test.

It is desirable that bituminous road binders and the like have what is known as good adhesion to aggregates, more particularly to hydrophilic aggregates exemplified by Massachusetts rhyolite and Louisiana slick gravel. Bitumens, and particularly asphalt, exhibit a tendency to strip from aggregates after having been mixed therewith.

Various means of inhibiting this stripping tendency have been proposed, among which the most satisfactory are those means whereby a small amount of an adhesion agent is added to the bituminous binder.

Many such adhesion agents are incompatible with oil-in-water type bituminous emulsions, being either insoluble in the aqueous phase or having a strong tendency to break the emulsion.

In my copending application Serial No. 350,053, filed August 2, 1940, now Patent 2,412,526, of which this application is a continuation-in-part, the use of alkali metal dichromates as adhesion agents for bituminous emulsions is described. These dichromates, while highly eliective as agents for this purpose, have a tendency to break, or to cause shot formation in quick-breaking emulsions.

It is an object of the present invention to provide a means of incorporating alkali metal ditheless stable on normal storage and handling prior to admixture with aggregate.

These and other objects of the invention will be apparent from the ensuing description and the appended claims.

In accordance with the procedure and in producing the product of the invention, a bituminous material is dispersed in alkaline water to produce a quick-breaking emulsion, and there is incorporated in the alkaline water, at a time before the water and bituminous material cease to be subjected to emulsifying conditions, a small amount, sufiicient to promote adhesion but insufficient to cause breakdown of the finished product, of an alkali metal dichromate.

By this means, a much better product is ob tained showing much less tendency to break down than is obtained by adding the dichromate to the emulsion after it has been formed.

The materials going into the product thus manuiactured are bituminous material, alkaline water, dichromate and an emulsifier or a material capable of reacting with the alkali to produce an emulsifier. As explained in more detail below, the emulsifier may be (and preferably is), the reaction product of the alkali contained in the water and saponifiable material contained in the bitumen, in which case emulsifier need not be added as a separate ingredient.

The bituminous material may be any liquid or heat-liquefiable carbonaceous material, such as natural asphalt, asphaltic residua from the distillation of petroleum, coal tar, coal tar pitch, road oils from petroleum, etc., but preferably it is an asphalt, which may, as stated, be a natural or an artificially produced product, and which may have a penetration (A. S. T. M. D-5 method) of 300 or higher to zero: Both steam refined and air blown asphalts may be used.

Most advantageously, an asphalt is used which contains saponifiable material of such kind and in such amount as to be emulsifiable in hot, dilute caustic alkali by the method of Montgomerie, United States Patent No. 1,642,675 or the method of Braun, United States Patent No. 1,737,491. Alternatively, and still within the preferred embodiment of the invention, an asphalt which is normally not so emulsifiable, but which has been modified in accordance with the procedure of Fratis and Oakley, patent application Serial No. 404,196, filed July 26, 1941, now Patent 2,406,823, may be used.

The alkaline water used in emulsification may be water rendered alkaline with any of a group of water-soluble alkalis forming water-soluble 3 salts, such as sodium and potassium hydroxide, trisodium phosphate, ammonia, water-soluble amines, water-soluble quaternary ammonium bases such as tetraethanol ammonium hydroxide, etc, Preferably, however, the alkali is sodium or potassium hydr'oxide.a The alkalinity of the wa-- ter before admixture with the dichromate is preferably within the approximate limits of pH 10.5

to 13. When potassium hydroxide is used as the alkali, the alkaline water, before emulsification and before addition of dichromate, preferably contains about 0.2 to 0.5% KOH'; that is, about 01 to 0.25% KOH based on finished emulsion containing 55% asphalt. Suitable proportions of other alkalis, and suitable proportions of alkali based upon finished emulsions containing other" proportions of asphalt, can be readily calculatedi The dichromate is preferably sodium dichromate, generally available as Na2Cr2Om2I-I2O, butpotassium dichromate serves equally well and lithium and ammonium dichromatesmayalso be i ever, an added soap-type or even non-soap" type 7 Thus, to the alkaline watermay beadded a small amount emulsifier maybe employed.

of rosirr'oil, oleic acid, alcohol-soluble;gasolineinsolubl'e pinewood' resins described and claimed" in United- States Patent 2,193,026 "to'Lucius Cole man Hall, or'a sodium orpotassiumsaltof the same, or a mixture ofsu chsaponifiable or saponi fied materials. Or a protein such as watersoluble blood ,(either water-soluble" dry blood, such as'describedin vMcKesson, UnitedStates Patent No.--2071;73lor 'liquid, homogenized coagulated blood such as described in Buckley and B1 y, UI lite d'- Sl3atS Patent N0. 2,372,658), may

be used asthe emulsifier. Other suitable emulsifiers will be apparent-to one skilledin the art. These emulsifiers should be used tin" such amount as to produce a quic'k-breakingemulsion;

stable on storage andhandling, but breaking:

quickly on contact-with aggregate. Theexaot proportion used in any given case will depend on factors such as the residue of the emulsion and the nature of the asphalt. Thus; emulsions of high residuerequir e more emulsifier-than emulsions of low residue, while asphalts which are substantially devoid of'saponifiable constituents will require more added emulsifier than' asphalts which contain a substantial amount of saponifiableconstituents. As an example, an asphalt from Mid-Continent crude containing'verylittle sapomfiable matter and incapableof emulsi fication by the Montgomerie or Braun process, will require 0.05 to 0.5%of Swedish'ro'sin oil to produce-a satisfactory, 55% residue asphalt emul sion. Choice of proper proportion ofemulsifier can be 'made readily by oneskilled in'the artdin,

any given case: I

Various procedures maybe used 'to produce the emulsions of the invention. Thusy molten" asphalt at about 230 to 280Ffmay be added to ahot (130to 180 F.) aqueous alkaline solution (containing added emulsifienif any) in' an open mix pot provided with a propeller-typeagitator. Emulsification will take place immediately. Or the procedure of Braun, United StatesPaten't ,No.

1,737,491 may be employed; that is, to a seed.

batch of previously formed emulsion. are added simultaneously the molten asphalt and hot aqueous alkali; and a portion of the emulsion thus produced is used as a seed batch for making a further quantity of emulsion. Or the molten asphalt and hot aqueous alkali may be fed simultaneously to a colloid mill, in which the ingredients are subjected to the powerful shearing forces of two surfaces moving relatively to one another. A suitable mill for this purpose isthe well known Charlotte mill. Preferably,

- however, an open mix pot is used.

In any case, the dichromate ingredient is incorporated in the mixture at a time before the water and bituminous material cease to be subjected to emulsifying conditions. Thus, the dichi'omate may be added to the alkaline water before the latter is mixed with the bitumen. Or three separate streams of ingredients may be fed to emulsifying apparatus containing a seed batch of emulsionythat is, a stream of bitumen, a stream of alkaline water and a stream of aqueous dichromate solution (which latter is conveniently of 10% strength), may be supplied simultaneously to'a seedbatch'of previously formed emulsion. Or the dichromate in solution form may be injected into the emulsifying apparatus at a point where'emulsification has already occurred or is proceeding, but where emulsifying conditions still prevail.

The important consideration, in any case, is that the dichromate be not added to the emulsion after it has been formed and is no longer subjected to theemulsifying action. By observing this precaution, breakdown of the emulsion or other harmful effects are avoided or greatly reduced.

to a seed batch of emulsion. V

The amount of dichromate incorporated in the emulsion should be sufiicient substantially to promote adhesion of the bitumen to aggregates but insufiicient to cause breakdown of the emulsion.

. Preferably, about 0.05 to 0.5% of dichromate,

based on weight of finished emulsion, is incorporated. Dichromates are rather strongly acidic; and if too much is added, the alkalinity of the emulsion may be reduced to a point where the emulsion is unstable.

As added precautions to prevent possible harmful effects of the dichromate on the stability and marketability of the emulsion, further to promote adhesion, and to prevent or delay phase separation (i. e., a settling of water to the bottom and a rise of bitumen to the top of the emulsion containeror the reverse), the following directions may be followed: A stabilizersuch as Swedish rosin oil or alcoholsoluble, gasoline-insoluble pinewood resins described and claimed inUnited States Patent 2,193,026 to Lucius Coleman Hall (as such or saponified) or a protein material such as blood, may be added to the emulsion after it has been made. This renders the emulsion more stable, but care should be taken not to use sufficient stabilizer to prevent rapid breakdown on contact with aggregate. Usually 0.05 to 0.15%"of added stabilizer is sufficient. The added stabilizer, as in the case of Swedish rosin oil and alcohol-soluble, gasoline-insoluble pinewood resins described andclaimed in United States Patent 2,193,026 to Lucius Coleman Hall, may

also improve adhesion. Also, a small amount,

usually about 0315 to 0.50%based on weight of finished emulsion, of bentonite clay may be added Preferably, the dichromate is' added' to the alkaline Water before admixture of the latter with the bitumen, or it is added as a third stream along with bitumen and alkalinewater' to the emulsion, or to the alkaline water prior to emulsification, to resist phase separation.

The following specific examples will serve further to illustrate the practice and advantages using 0.32% aqueous NaOH as the aqueous phase and employing the procedure of Braun, United States Patent No. 1,737,491. In one case no dichromate was added while in another'case a 10% of the invention. aqueous solution of sodium dichromate was fed Example I .-Three emulsions were prepared to the emulsifying apparatus simultaneously with approximately as follows: Emulsion A was an the hot asphalt and hot aqueous alkali, in amount emulsion of a 200 penetration Venezuelan asphalt. suificient to incorporate 0.5% NazCrzOv in the The asphalt was heated to 250 F. An aqueous emulsion. Both emulsions were of good quality, KOH solution was prepared and to it was added the emulsion containing dichromate being in no a 10% aqueous solution of sodium dicromate. Almanner inferior to the emulsion containing no kalinity of the KOH solution was determined by dichromate. In addition, the emulsion containtitration before and after addition of dichromate. ing dichromate exhibited greatly improved ad- This aqueous KOH solution, to which had been hesion on Louisiana slick gravel and Greenbrae added sodium dichromate, was heated to 140 F. (Marin County, California) aggregate, both of and placed in an open mix pot provided with a which are hydrophilic aggregates to which propeller-type agitator. The propeler was set asphalt adheres poorly. in motion and was operated at high speed while Example III.-Quick-breaking emulsions were the hot asphalt was poured in in quantity sufilmade of an 80-6 road oil by the method of Braun. cient to produce the desired residue. Emulsions In several cases, sodium dichromate was added B and C were similarly prepared, but to differto the alkaline water before emulsification; in ent residues, and Emulsion C was made from an other cases, the dichromate was added to the asphalt of about 350+ penetration. emulsifying apparatus in the form of a 10% solu- Tests were made of these emulsions, with retion, simultaneously with the road oil and alsults as given in the table, below. kaline water. A control sample (no dichromate) Table ass dime Emulsion water before ggg g water after g g g g Adhesion adding Finished adding Dichromate Emulsion Dichromate Per cent 0. l3 0. 20 0. 0s 57 85-100 0. l3 0. 2o 0. 06 62 80-95 0. l3 0. 175 0.07 66 80-95 1 Based on finished emulsion.

KOH was determined by titration with 0.1 N 5 was similarly prepared. Adhesion tests were HCl, using phenolphthalein as indicator. Resmade on the emulsion, with results as follows: idue was determined by the procedure of A. S.

T. M. D244-42. Adhesion was determined as fol- P C t g h lows: 200 grams of dry standard Massachusetts er 611 How Added A esion rhyolite, graded so as to pass entirely through a 3 252? 4-inch (No. 3) sieve and to be retained completely on a No. 10 sieve, were taken. This agni1 5 gregate was heated to 300 F. and mixed with 16 g- 1 5 water 32 grams of emulsion until complete coating resulted. oIsII' an 75 Three 50 gram samples of the coated aggregate j f giggg f Simultanewsly were then taken and each was spread thinly on 0.2 dn 5 a. metal can lid and left in an oven for 48 hours at 140 F. Each cured sample was then dropped into 400 cc. of boiling distilled water in a 600 cc. Based on finished 611111151011- beaker and stirred 3 minutes at the rate of 60 I claim:

times a minute, boiling meanwhile being con- 1. A method of preparing a quick-breaking, tinued. Each beaker was then removed from the free-flowing, oil-in-water type bituminous emulheat, and, after ebullition had ceased, cold water sion having an A. S. T. M. D-244 demulsibility of was run into the beaker through a submerged not less than about 60%, stable in storage and hose until any film of asphalt on the surface of handling and stable in storage against the incorthe water was flushed out. Each sample of agporation therein of as much as 0.5% by weight of gregate was then removed and placed on abthe emulsion of ammonium and alkali metal sorbent paper and air dried. The dried samples dichromates, comprising emulsifying a bitumiwere then inspected visually by an experienced nous material in water to produce a quick-breakobserver to estimate the percentage area coated, ing bitumen-in-water emulsion and incorporatuncoated area being deemed that retaining no ing in the emulsion, at a time before the water asphaltic coating. The figures for the three and bituminous material cease to be subjected to samples were then averaged. emulsifying conditions, a small amount of a salt Example II .A 55% residue emulsion of a 200 selected from the group consisting of ammonium Penetration California asphalt was P p dichromate and alkali metal dichromates, said bituminous :emulsi'o'na comprisingzby weight about I 55-70% bituminouse materialg 30+50% of water.

and: ;05'0.5% .of said salt. I

2.1 The methodzofnclaimi 1'; wherein the .bituminous material is asphalt...

3. Themethod ofclaim: '1, wherein-the water is rendered alkalinewby:causticalkali and has apH of about 10.54 13:beforeiincorporation.of the-dichromate.

4; Theimethod of 1claim-1,-:w-herein the emulsification isrcarried out'by separately: but simultaneously; supplying; heated bitumen, an aqueous solution of said dichrom'ate salt and an aqueous solution of caustic alkali toa-bocly ofpreformed bitumenein-Water emulsion.

5.: A" method. of" preparin'gw-a' quick-breaking, free-flowing, oil-in-water type asphalt emulsion havingran A; S. :T.- M1 ,D-24 l demulsibility of not less than about 60%; stable-in storage and handling'andstable in storage against ,theincorporation therein ofas muchlas 0.5 by-weight of the emulsion of" ammonium and alkali metal (11- chromates, comprising I emulsifyingan asphalt in dilute, aqueous caustic alkali, said asphalt being of the type which -emulsifies in dilute, aque-- ous caustic alkali, and incorporating in the emulsion 0.050.5% by weight of the emulsion of a salt selected from the group consisting of ammonium dichromate and alkali metal dichromates, said salt being incorporated in the emulsion byadding it at a time not later than the time of juncture of the asphalt and aqueous caustic alkali, said emulsion comprising by weight about-155 70% of asphalt and 30-50% of water.

6. The method of claim 5, wherein emulsification is carried out by separately but simultaneously supplying heated asphalt, an aqueous solution of the said dichromate salt and a heated aqueous solution of caustic alkali to a body of preformed asphalt-in-water emulsion.

'7. The method of claim 5, wherein the emulsifying agent consists essentially of the reaction products of the asphaltic acids naturally present in the asphalt and the aqueous caustic alkali.

8." A quick-breaking, liquid; free-flowing, oilin-water' type bituminous emulsion having an A. S. T. M. D244demulsibility of not less than about 60%, stable in storage and handling and stable, in storage againstthe'incorporation Ttherein of as much as 0.5%, by weight of the emulsion, of ammonium and alkali metal dichromates, said emulsion comprising by-weight about 55-70% of" bituminous material, 30-50% of water, and 0.05 0.5% of a salt selected-fromnthe'group consisting of alkali metal dichromates and ammonium dichromate; 'saidtsalt having been incorporated.

in the emulsions at a; time: before .the water and the bituminous mater-ialz.cease tov be subject to emulsifying conditions:

9. A quick-breaking, liquid, free-.fiowing,;,oilin-water ;type--bituminousemulsion having, an A. S. T; M. D-,- 244-.deI nulsibi1ity of not-lessthan about-60%, stable instorage against the'incorporation' therein of as :much as 0.5%, by weight lo-rof the emulsion,-=ofammonium and alkali metaldichromates, said emulsion comprising, vbyeweight about 55-70%' of: a bitumen; 30=50% of water,

and 005- --of; a:.salt selected from the group;-

consisting of alkali imetalv dichromates and am- 5 gmonium dichromate'saidsalt having been incorporatedin the emulsion: by separately *butsimultaneously supplyinggheated bitumen, an aqueous solution ofgsaiol: dichromatesalt and an aqueous solution ot=caustic alkali to abody preformed; bitumen-in-water emulsion."v

10; A quick-breaking; liquid;free-flowing,1oilin-water' type asphalt emulsion having I, an- A. S. T. M. D-244-demulsibility'of-notless than about 60%, stable in storage and handling: and

i;stab1e in storage against the-incorporation therein of as much as 0.5%, by Weight of the emulsion, of ammonium and alkali metal dichromates, said emulsion comprising by weight about 55-70% of asphalt, -50% of..water, and 0.05-0.5% of a salt 3.41 selected from the group consisting of alkali metal dichromates and; ammonium dichrom-ate, said asphalt being of Ethe type which emulsifies in diluteaqueous caustic alkalLl theaqueous continuous phaseof the 'emulsion containing about 01-05% by weight of the emulsion, of caustic alkali, and said di'c'hromate saltbeing'incorpo rated in the emulsion by adding it at a time not later thanxthe time of juncture of the asphalt and aqueous caustic alkali.

PAUL E. MCCOY.

REFERENCES CITED The following references are of record in the file of. this. patent:

UNITED SIfrTE-S Z PATENTS 

1. A METHOD OF PREPARING A QUICK-BREAKING, FREE-FLOWING, OIL-IN-WATER TYPE BITUMINOUS EMULSION HAVING AN A.S.T.M. D-244 DEMULSIBILITY OF NOT LESS THAN ABOUT 60%, STABLE IN STORAGE AND HANDLING AND STABLE IN STORAGE AGAINST THE INCORPORATION THEREIN OF AS MUCH AS 0.5% BY WEIGHT OF THE EMULSION OF AMMONIUM AND ALKALI METAL DICHROMATES, COMPRISING EMULSIFYING A BITUMINOUS MATERIAL IN WATER TO PRODUCE A QUICK-BREAKING BITUMEN-IN-WATER EMULSION AND INCORPORATING IN THE EMULSION, AT A TIME BEFORE THE WATER AND BITUMINOUS MATERIAL CEASE TO BE SUBJECTED TO EMULSIFYING CONDITIONS, A SMALL AMOUNT OF A SALT SELECTED FROM THE GROUP CONSISTING OF AMMONIUM DICHROMATE AND ALKALI METAL DICHROMATES, SAID BITUMINOUS EMULSION COMPRISING BY WEIGHT ABOUT 55-70% BITUMINOUS MATERIAL, 30-50% OF WATER AND 0.05-0.5% OF SAID SALT. 